Novel functionalized resin derived from polyallylamine

ABSTRACT

A new functionalized resin represented by the general formula was derived from polyallylamine. ##STR1## [wherein; X represents the general formula ##STR2## (t is 0 or 1, l is an integer of 1 to 20), n≧10, 0&lt;j&lt;1, u=1 or 2, and m=1 or 2, with the proviso that t and m are not simultaneously 0]. 
     The functionalized resin is preferably used for recovering heavy metals in waste water and for optically dissolving amino acids.

This is a divisional of co-pending application Ser. No. 670,545, filedon Nov. 13, 1984, now U.S. Pat. No. 4,604,451.

FIELD OF THE INVENTION

The present invention relates to a novel functionalized resin derivedfrom polyallylamine, and more particularly to a functionalized resinhaving amino acid moieties introduced in side chains of thepolyallylamine.

DESCRIPTION OF THE PRIOR ART

A number of reports are found on the synthesis of functionalized resinshaving α-amino acid moieties in side chains thereof. Processes forsynthesizing these resins are roughly classified into two categories.One of them comprises preparing a vinyl compound having an amino acidmoiety, followed by polymerizing it to form a functionalized resin. Theother comprises selection of an appropriate resin as a carrier, andreaction of the resin with a suitably modified compound having anα-amino acid moiety to yield a functionalized resin.

As an example of the former category, there has been reported a processfor producing polymers by reacting one or more of various amino acidswith acrylic acid or to methacrylic acid to form a monomer, andpolymerizing the resulting monomer. Such polymers include, for example,those of acryloyl or methacryloyl proline, valine, glycine, lysine, andtryptophan (see, e.g. N. Sakota et al., J. Poly. Sci. Poly. Lett. Ed.,12, 503 (1974); Y. Imanishi et al., Makromol, Chem., 177, 1401 (1976);A. Watanabe et al., J. Chem. Soc. Japan, 91, 874 (1970); K. Kondo etal., Makromol Chem., 176, 1307 (1975); and H. Sumita, Kobunshi, 17, 139(1968)).

However, prior art processes of the former category for producingfunctionalized resins cannot be regarded as practically useful, since aside reaction such as a partial polymerization of the monomer will takeplace during its preparation and this will bring about difficulties inthe isolation and purification of the monomer. In addition, when theresulting resins are used for certain purposes, it is not alwaysfavourable method that the resins have the large number of active sitesin a polymer molecules.

There is known, as an example of the latter category, a process forproducing a functionalized resin by bonding cystine to apoly(p-chloromethylstyrene) carrier.

In order to enhance the reactivity of functionalized resin havingfunctional groups in side chains thereof, it is generally necessary tofacilitate the association of reaction site in side chains withmolecules of the reaction partner. Thus it is desirable that the sidechain be long to some extent and flexible or free to bend. Accordingly,for the purpose of enhancing the reactivity of α-amino acid moiety inthe above-mentioned functionalized resin, the use of a carrier resinhaving functional groups which is bonded with the backbone of the resinthrough a flexible methane or polymethylene group is preferred to theuse of a resin such as known p-chloromethylstyrene resin having benzenerings in side chains that are rigid and bulky.

Further, as amino acids used, those which are cheap and available inlarge quantities are more profitable, and glutamic acid and asparticacid meet such requirements. On the other hand, it is required for thecarrier resin to have basic functional groups in side chains, forexample, like polyamines, because glutamic acid and aspartic acid havecarboxyl groups at the γ- and β-positions, respectively.

However, there is no report of successful synthesis of such afunctionalized resin, because the synthesis of a polyamine containing noaromatic nucleus is extremely difficult and no effective and economicalroute has not yet been established for selective reaction of theγ-positioned carboxyl group of glutamic acid.

SUMMARY OF THE INVENTION

An object of the invention is to provide a novel funtionalized resinhaving amino acid moieties in side chains, which is derived frompolyallylamine.

Another object of the invention is to provide an economical process forproducing such a functionalized resin.

Other objects and advantages of the invention will be apparent from thefollowing detailed description.

DETAILED DESCRIPTION OF THE INVENTION

As a result of extensive studies, the present inventors have beensucceeded in obtaining functionalized resins, represented by thefollowing general formula (I) from a starting material polyallylamine,economical production of which had been accomplished first by one(Harada) of the present inventors. ##STR3## [In formula [I], Xrepresents the formula [II]: ##STR4## (wherein t is 0 or 1 and l is aninteger of 1 to 20), n≧10, o<j<1, u=1 or 2, and m=0 or 1, with theproviso that t and m are not simultaneously 0.]

The resins represented by the above formula [I] are roughly divided intothe following three types of polymers: ##STR5##

The above polymer A is obtained by reacting polyallylamine withN,N-phthaloylglutamic 1,5-anhyhdride represented by the formula:##STR6## or with N,N-phthaloylaspartic 1,4-anhydride represented by theformula: ##STR7## and then treating the intermediate product withhydrous hydrazine such as hydrazine hydrate.

Of these two N,N-phthaloylamino acid anhydrides, N,N-phthaloylaspartic1,4-anhydride [IV] reacts at the sites of both α- and β-carboxyl groupsand hence it is difficult to effectively introduce intended α-amino acidmoieties in side chains. Therefore, the use of this amino acid anhydrideis disadvantageous compared with the use of N,N-phthaloyl-glutamic1,5-anhydride [III] which reacts only at the γ-carboxyl group, and thepolymers produced by using the former anhydride have restrictedapplications.

It is also possible that the γ-carboxyl group of glutamic acid or theβ-carboxyl group of aspartic acid is activated by some methods otherthan the above. For example, the amino acid can be converted into anester (active ester) by reacting with p-nitrophenol, pentachlorophenolor N-hydroxysuccinimide, or can be converted into the acid halide, andthereafter the product (ester or acid halide) can be reacted withpolymines of the general formula [I] (m=0). In this case, the α-aminoacid moieties should be protected so as not to participate in saidreaction. For the protection reactions and the protecting agents therecan be utilized techniques which are utilized in the synthesis ofpeptides. Although being obtainable also according to the abovementioned methods using the ester or acid halide, the functionalizedresin [I] of the invention is better synthesized through the route inwhich compound [III] or [IV] is used, because the above mentionedmethods using the ester or acid halide require the complication ofoperations for the temporary protection of α-amino acid moieties.

The polymer B is obtained by reacting polyallyl-amine with aphthaloylamino acid, acid chloride thereof, or an acid anhydride(including asymmetric acid anhydrides derived from phthaloyl amino acidand other carboxylic acid), followed by treating the intermediateproduct with hydrous hydrazine such as hydrazine hydrate.

The polymer C is obtained by reacting the thus obtained polymer B withthe compound such as N,N-phthaloylglutamic 1,5-anhydride (III) andN,N-phthaloylaspartic 1,4-anhydride (IV), followed by treating theintermediate product with hydrous hydrazine such as hydrazine hydrate.

The functionalized resin [I] of the invention can be used to recoverheavy metals dissolved in water or to resolve racemates of amino acid orthe like, by taking advantage of the metal chelating function of theα-amino acid structural parts thereof.

For use in such purposes, a functionalized resin [I] can be producedaccording to the process of the invention from an crosslinkedpolyallylamine.

The following examples illustrate the invention, but it is not limitedto these examples.

Polyallylamine used in the following examples was prepared frompolyallylamine hydrochloride which had been synthesized according to theprocess described in Japanese Patent Application No. 54988/83. That is,an aqueous solution of polyallylamine was prepared by passing an aqueoussolution of 20% polyallylamine hydrochloride through a strong-basic ionexchange resin column. In most of the following experiments the aqueoussolution of polyallylamine was used as such, but in other experiments apure poly-allylamine obtained by freeze-drying of the aqueous solutionwas used in the form of methanolic solution.

REFERENCE EXAMPLE 1 Preparation of phthaloylglutamic 1,5-anhydride

(1) In a solution of Na₂ CO₃ (51.5 g) in water (350 ml) at 5° C. wasdissolved L-glutamic acid (29.4 g). Carboethoxy phthalimide (59.6 g) wasadded to the solution and suspended therein and thereafter reacted at350° C. for 30-40 minutes. Then the solution was freed from insolublematter, adjusted to pH 2.5 with 6N-HCl, and allowed to stand at 0° C.The resulting precipitate was filtered, and recrystallized from water togive N,N-phthaloylglutamic acid, yield 35.7 g, 64.4%; specific rotation[α]_(D) ²⁵ =-48.6°(C=1, dioxane).

(2) To phthaloylglutamic acid (27.7 g) obtained in (1) above was addedacetic anhydride (40 ml) and they were reacted at 40°-42° C. for 3hours. Then acetic anhydride (10 ml) was further added to react for 3additional hours. After reaction, the resultant mixture was allowed tocool, washed well with ether-petroleum ether, and dried under reducedpressure to give phthaloylglutamic 1,5-anhydride, yield 21.8 g, 84.2%;specific rotation [α]_(D) ²⁵ =-44.5°(C=1.75, dioxane).

REFERENCE EXAMPLE 2

Following the procedure of Reference Example 1, there were obtainedN,N-phthaloyl aspartic acid and 1,4-anhydride thereof from asparticacid.

EXAMPLE 1 Preparation of Polymer A

(i) A solution of polyallylamine hydrochloride (4.68 g) in water (50 ml)was passed through an Amberlite-402 column to prepare an aqueoussolution of polyallylamine. This solution was concentrated to a volumeof about 10 ml, and acetic acid of 9 times the volume of the solutionwas added. Then N,N-phthaloylglutamic 1,5-anhydride (12.96 g) fromReference Example 1 was added to the mixture and they are reacted at60°-65° C. for 1.5 hours. The reaction mixture was then allowed to cool,and poured into ethyl acetate. The formed precipitate was collected byfiltration, and dried to give poly[γ-allylamine(N-phthaloyl)glutamicacid](11.26 g).

IR absorption spectrum to this polymer showed absorptions at 1700 cm⁻¹and 1640 cm⁻¹ assigned to C=O and NHCO, respectively. The specificrotation [α]I_(D) ²⁵ was -35.5°(C=1, DMSO). The molar fraction ofphthaloyl-glutamic acid attached was about 50%, as determined from IRand UV absorption spectra and specific rotation.

From the above data, this polymer is concluded to have the followingstructure: ##STR8##

(ii) After poly[γ-allylamide(N-phthaloyl)glutamic acid](1.0 g) from (1)above was dissolved in DMSO (50 ml) by heating, hydrazine hydrate (10 g)was added thereto, and the mixture was stirred at room temperature for22 hours. The formed precipitate was filtered, washed with DMSO and thenwith water, and dissolved in 1N-HCl (19 ml) at room temperature. Thesolution was poured into acetone, and the formed precipitate wascollected by filtration, and dried to give poly(γ-allylamideglutamicacid) (0.65 g).

IR absorption spectrum of this polymer showed absorptions at 1720 cm⁻¹and 1640 cm⁻¹ assigned to C═O and NHCO, respectively. The specificrotation [α]_(D) ²⁵ was 14.1°(C=1, H₂ O). UV absorption spectroscopy andproton NMR absorption spectroscopy indicated that the polymer had noaromatic nucleus. From these results, it is concluded that the polymerhas the following structure: ##STR9##

EXAMPLE 2 Preparation 1 of Polymer B

(i) A mixture of phthalic anhydride (500 g) and β-alanine (267 g) wasfused by heating at 200° C. for 15 minutes, and poured into water (1500ml). The formed precipitate was collected by filtration, andrecrystallized from ethanol to give phthaloyl-β-alanine (hereinafterreferred to as pht-βAla), yield 537 g, 81.6%.

Then Pht-βAla (43.9 g) was mixed with thionyl chloride (82 ml) and theywere reacted by heating at 50° C. for 30 minutes. The resultant mixturewas allowed to cool, and the excess of thionyl chloride was distilledoff. The residue, solidified entirely, was purified with petroleum etherto tive N-phthaloyl-β-alanine chloride (hereinafter referred to asPht-βAlaCl), yield 45.8 g, 96.4%.

A solution of Pht-βAlaCl (45.8 g) in acetone was added dropwise to amixture of a 13.6% aqueous polyallylamine solution (81.7 g),triethylamine (21.6 g), and acetic acid (247 ml) under cooling with ice,and they were reacted for 6 hours. Then the acetone was removed bydistillation under reduced pressure, and the residue was poured intoethyl acetate (3000 ml). The formed precipitate was collected, andpurified with methanol-ethyl acetate to give poly [β-allylamide(N-phthaloylamino) β-alanine], yield 39.0 g.

The resin was treated with conc. HCl and with acetone, and filtered anddried. Results of IR absorption spectroscopy (absorptions at about 1700cm⁻¹ and about 1640 cm⁻¹ assigned to C═O and NHCO, respectively), UVabsorption spectroscopy (an absorption in 200-250 nm assigned tophthaloyl groups), and elementary analysis have revealed that this resinis N-phthaloyl-polyamidepolyamine having the following structure:##STR10##

(ii) Phthaloyl-containing polyamidepolyamine (10.0 g) from (i) above wasdispersed in DMSO (100 ml), and hydrazine hydrate (50 ml) was addedthereto and they were reacted at 60° C. for 10 hours. Then the resultingprecipitate was filtered, and dissolved in a mixture of conc. HCl (20ml) and water (10 ml). The solution was poured into acetone (500 ml),and the precipitated polymer was filtered and dried.

IR absorption spectrum of this polymer (absorptions at about 1700 cm⁻¹and about 1640 cm⁻¹ assigned to C═O and NHCO, respectively) and UVabsorption spectrum thereof (no absorption assigned to the phenyl groupwas observed) have indicated that this polymer is concluded to be apolyamine having the following structure: ##STR11##

EXAMPLE 3 Preparation 2 of Polymer B

(i-a) N-phthaloylglycine chloride (hereinafter referred to asPht-Gly-Cl) (22.4 g) prepared according to the procedure of Example2-(i) was dissolved in acetone (40 ml). The solution was added dropwiseto a mixture of a 13.6% aqueous polyallylamine solution (42.0 g),triethylamine (10.1 g), and acetic acid (126 ml). Then a resin (16.5 g)was obtained in the same manner as in Example 2-(i), yield 16.5 g.

(i-b) To Pht-Gly-Cl (22.7g) and acetic acid (6.0 g) dissolved intetrahydrofuran (130 ml) was added dropwise triethylamine (14 ml).Regardless of immediate appearance of a precipitate, the reaction wascontinued overnight. The resulting precipitate was filtered, and thefiltrate containing glycylacetic anhydride was used as such in the nextstep.

Acetic acid (100 ml) was added to a solution of polyallylaminehydrochloride (9.4 g) in water (30 ml). Regardless of immediateprecipitation of a polymer, a solution of triethylamine (10.1 g) inacetic acid (50 ml) was added to the mixture, giving a homogeneoussolution [a triethylamine-treated polyallylamine solution (PAA-Et₃ Nsolution)].

On addition of the above solution of glycylacetic anhydride to thePAA-Et₃ N solution, a polymer precipitated immediately. After 3-hourcontinuation of the reaction, the precipitate was filtered, anddissolved in a mixture of conc.HCl (20 ml) and water (20 ml). Thesolution was poured into acetone (1500 ml), and the formed precipitatewas filtered and dried.

(i-c) To Pht-Gly-Cl (24.6 g) and phthaloylglycine (22.6 g) dissolved intetrahydrofuran (200 ml) was added dropwise triethylamine (15.4 ml)under cooling with ice. While a precipitate appeared simultaneously withthe addition, the reaction was continued for 1-2 hours. Then theprecipitate was filtered, and the filtrate containing diphthaloylglycinewas used as such in the next step.

A solution (50 ml) of triethylamine (10.1 g) in acetic acid was added toa dispersion of polyallylamine hydrochloride (9.4 g) in acetic acid (100ml). Then water (30 ml) was added to the mixture to form a homogeneoussolution.

On addition of a solution of diphthaloylglycine anhydride intetrahydrofuran to the resulting solution, a polymer precipitatedimmediately. The reaction was continued at room temperature. Then thesupernatant was removed by decantation, and the residue was washed withtetrahydrofuran and then with ethyl acetate and dissolved in conc. HCl(40 ml). The polymer was reprecipitated from the solution with acetone(1500 ml).

IR absorption spectrum (absorptions at about 1700 cm⁻¹ and about 1640cm⁻¹ assigned to C═O and NHCO, respectively) and UV absorption spectrum(an absorption in 200-250 nm assigned to phthaloyl groups) of the resinsprepared in (i-a), (i-b), and (i-c) have revealed that all the resinsare N-phthaloyl-polyamidepolyamines of the following structure:##STR12##

(ii) Each (10.0 g) of the phthaloyl-containing polyamidepolyaminesobtained in (i-a), (i-b), and (i-c) was dispersed in DMSO (100 ml) andreacted with hydrazine hydrate (50 ml) at 60° C. for 10 hours. Then theprecipitate was filtered, and dissolved in a mixture of conc. HCl (20ml) and water (10 ml). The solution was poured in acetone (500 ml), andthe precipitated polymer was filtered and dried.

From IR absorption spectrum of the thus obtained polymers (absorptionsat about 1700 cm⁻¹ and about 1640 cm⁻¹ assigned to C═O and NHCO,respectively) and UV absorption spectrum thereof (no absorption assignedto the phenyl group was observed), these polymers are concluded to bepolyamines having the following structure: ##STR13##

EXAMPLE 4 Preparation 3 of Polymer B

(i) A mixture of phthalic anhydride (148 g) and γ-amino-n-butyric acid(103 g) was fused by heating at 180° C. for 5 minutes and then at 200°C. for 5 minutes, and poured into water (750 ml) to obtain N.sup.γ-phthaloylamino-n-butyric acid, yield 191.8 g, 82.2%.

This acid (35.0 g) was reacted with thionyl chloride (62 ml) at 50° C.for 40 minutes. After reaction, the excess of thionyl chloride wasdistilled off. After addition of petroleum ether to the residue andcooling thereof, N.sup.γ -phthaloylamino-n-butyric acid chloride wasobtained, yield 36.9 g, 97.6%.

The N.sup.γ -phthaloylamino-n-butyric acid chloride (36.9 g) as such wasadded to a mixture of a 13.6% aqueous polyallylamine solution (61.3 g),triethylamine (14.8 g), and acetic acid (184 ml). The acid chloride wasdissolved not immediately but gradually and completely in about 20minutes from the addition, forming a homogeneous solution. The resultantsolution was poured into ethyl acetate (1500 ml). The formed precipitatewas filtered, and dissolved in a mixture of conc. HCl (50 ml) and water(20 ml). The solution was poured into acetone (1000 ml), and the formedprecipitate was collected by filtration, yield 20.2 g.

From IR absorption spectrum of the thus obtained resin (absorptions atabout 1700 cm⁻¹ and about 1640 cm⁻¹ assigned to C═O and NHCO,respectively) and UV absorption spectrum thereof (an absorption in200-250 nm assigned to phthaloyl groups), the resin is concluded to bean N-phthaloyl-polyamide polyamine having the following structure:##STR14##

(ii) Phthaloyl-containing polyamide polyamine (10.0 g) from (i) abovewas dispersed in DMSO (100 ml) and reacted with hydrazine hydrate (50ml) at 60° C. for 100 hours. Then the resulting precipitate wasfiltered, and dissolved in a mixture of conc. HCl (20 ml) and water (10ml). The solution was poured into acetone (500 ml), and the precipitatedpolymer was filtered and dried.

From IR absorption spectrum of the thus obtained polymer (absorptions atabout 1700 cm⁻¹ and about 1640 cm⁻¹ assigned to C═O and NHCO,respectively) and UV absorption spectrum thereof (no absorption assignedto the phenyl group was observed), this polymer is concluded be apolyamine having the following structure: ##STR15##

EXAMPLE 5 Preparation 4 of Polymer B

(i) A mixture of phthalic anhydride (62.1 g) and ε-amino-n-caproic acid(50 g) was fused by heating at 180° C. for 10 minutes, and poured intowater (750 ml) to give N.sup.ε -phthaloylamino-n-caproic acid, yield96.1 g, 96.5%.

Then N.sup.ε -phthaloylamino-n-caproic acid (39.2 g) was reacted withthionyl chloride (62 ml) at 50° C. for 5 minutes. Thereafter the excessof thionyl chloride was distilled off. Petroleum ether was added to theresidue, and the mixture was cooled to give N.sup.ε-phthaloylamino-n-caproyl chloride, yield 39.9 g, 95.1%.

A solution of N.sup.ε -phthaloylamino-n-caproyl chloride (39.9 g) inacetone was added to a mixture of a 13.6% aqueous polyallylaminesolution (60.0 g), triethylamine (14.5 g), and acetic acid (181 ml).After this reaction, a polymer was obtained by the same post-treatmentas in Example 4 (i), yield 22.1 g.

From IR absorption spectrum of the obtained resin (absorptions at about1700 cm⁻¹ and about 1640 cm⁻¹ assigned to C═O and NHCO, respectively)and UV absorption spectrum thereof (an absorption in 200-250 nm assignedto phthaloyl groups), the resin has been confirmed to beN-phthaloyl-polyamidepolyamine having the following structure: ##STR16##

(ii) Phthaloyl-containing polyamide polyamine (10.0 g) from (i) abovewas dispersed in DMSO (100 ml), and reacted with hydrazine hydrate (50ml) at 60° C. for 10 hours. Then, the resulting precipitate wasfiltered, and dissolved in a mixture of conc. HCl (20 ml) and water (10ml). The solution was poured into acetone (500 ml), and the precipitatedpolymer was filtered and dried.

From IR absorption spectrum of the obtained polymer (absorptions atabout 1700 cm⁻¹ and about 1640 cm⁻¹ assigned to C═O and NHCO,respectively) and UV absorption spectrum thereof (no absorption assignedto the phenyl group was observed), the polymer is concluded to bepolyamine having the following structure: ##STR17##

EXAMPLE 6 Preparation of Polymer C

Each (5 g) of polyamine hydrochlorides (B-1), (B-2), (B-3), and (B-4)prepared in Examples 2, 3, 4, and 5, respectively, was dissolved inwater (50-80 ml), and passed through an Amberlite-402 column to give anaqueous polyamine solution. This solution, after concentration to avolume of 10-20 ml, was reacted with N,N-phthaloylglutamic 1,5-anhydride(1.1 equivalent to the amino groups) at 60°-65° C. for 1-3 hours. Then,the reaction mixture was allowed to cool, and poured into ethyl acetate.The formed precipitate was filtered, and treated with conc. HCl-acetone.In this way, there were obtained polyamine hydrochlorides which havephthaloylglutamic acid moieties in side chains of different lengths.

From IR absorption spectra of the thus obtained polymers (absorptions atabout 1700 cm⁻¹ and about 1640 cm⁻¹ assigned to C═O and NHCO,respectively) and UV absorption spectra thereof (an absorption in200-250 nm assigned to phthaloyl groups), it has proved that thesepolymers have the following respective structures:

    __________________________________________________________________________    Starting                                    Specific rotation                 material                                                                           Structure of product                   [α].sub.D.sup.25 (c =                                                   1, DMSO)                          __________________________________________________________________________    (B-1)                                                                               ##STR18##                             -32.3°                     (B-2)                                                                               ##STR19##                             -34.1°                     (B-3)                                                                               ##STR20##                             -31.0°                     (B-4)                                                                               ##STR21##                             -28.6°                     __________________________________________________________________________

(ii) Each (1.5 g) of resins (C-1'), (C-2'), (C-3') and (C-4') preparedin (i) above was dissolved in DMSO (50 ml) by heating, and mixed withhydrazine hydrate by stirring at room temperature for 24 hours. Theformed precipitate was filtered, washed with DMSO and then with water,and dissolved in 1N-HCl (20 ml). The solution was poured into acetone,and the formed precipitate was filtered and dried. In this way, therewere obtained resins (0.7-0.8 g) to which glutamic acid moieties wereattached.

IR absorption spectra of these polymers (absorptions at about 1700 cm⁻¹and about 1640 cm⁻¹ assigned to C═O and NHCO, respectively) and UVabsorption spectra thereof (the absorption peak assigned to the phenylgroup which was observed in the spectra of the resins prepared in (i)above had disappeared) have indicated that the intended removal ofphthaloyl groups was completely carried out in the preparation of thesepolymers.

Results of characterization of these polymers are as follows:

    __________________________________________________________________________    Starting                                    Specific rotation                 material                                    [α].sub.D.sup.25 (c =                                                   1, H.sub.2 O)                     __________________________________________________________________________    (C-1')                                                                              ##STR22##                              13.0°                     (C-2')                                                                              ##STR23##                              13.6°                     (C-3')                                                                              ##STR24##                              12.8°                     (C-4')                                                                              ##STR25##                              12.5                             __________________________________________________________________________

What is claimed is:
 1. A process for producing a functionalized resinrepresented by the general formula: ##STR26## wherein n≧10, O<j<1 andu=1 or 2, comprising reacting polyallylamine with N,N-phthaloylglutamic1,5-anhydride represented by the formula ##STR27## orN,N-phthaloylaspartic 1,4-anhydride represented by the formula ##STR28##and treating the resulting polymer with hydrous hydrazine.
 2. A processfor producing a functionalized resin represented by the general formula##STR29## wherein l is an integer from 1 to 20, n≧10 and O<j<l,comprising reacting polyallylamine with a phthaloylamino acid, chloridethereof, or acid anhydride thereof, and treating the resulting polymerwith hydrous hydrazine.
 3. A process for producing a functionalizedresin represented by the general formula: ##STR30## wherein l is aninteger from 1 to 20, n≧10, O<j<1, and u=1 or 2, comprising reacting thefunctionalized resin defined in claim 2 with N,N-phthaloylglutamic1,5-anhydride or N,N-phthaloylaspartic 1,4-anhydride, followed bytreating the resulting polymer with hydrous hydrazine.